Sulphonated alkyl-aryloxyalkylols



Patented Feb. 1', 1938 2,106,716

UNITED STATES PATENT OFFICE SULPHONATED ALKYL-ARYLOXY ALKYLOLS Herman A.Bruson, Philadelphia, Pa., assignor to Riihm & Haas Company,Philadelphia, Pa.

No Drawing. Application December 30, 1936,

Serial No. 118,267

14 Claims. (01. 260-9912) v This invention relates to products obtainedby ing agents for dyes, pigments, clays, sulfur and sulfating andsulfonating ether alcohols of the other pulverulent materials, asspreading agents general formula I for insecticides or oily materialsand as leveling R o agents in dyeing operations. Those members of 5 A. R(0H): this group of compounds which contain twelve to in which A is analkyl group containing at least eighteen carbon atoms in the radicaldesignated eight carbon atoms, R is a benzene or naphthaby A are usefulas detergents and emulsifying lene nucleus which may have inorganic ororagents. They are very efiicient for these purganic substituents inaddition to that represented poses under conditions usually obtaining incomby A, R is a member of the group consisting of I merclal work becausethey do not form insoluble 1g alkylene radicals containing at least twocarbon salts with the calcium and magnesium found in atoms andpolyalkylene ether radicals in which hard-waters. the alkylenegroupscontain at least two carbon In practicing this invention, the alkylatedaroatoms, and a: represents a whole number less matic ether alcohol istreated with a sulfonating 5 than 3. 1 agent which is stronger than 100%sulfuric acid,

In the copending application of Bruson and suchas sulfurtrioxide,chlorsulfonlc acid or fum- Stein, Serial No. 97,347, filedAugust 22, 1936, a ing sulfuric acid, preferably at temperaturesbemethod is described whereby the hydroxyl groups tween 0 and 50 C., theamount of sulfonating of the radical B, when it is an alkylene group,agent depending on the number of sulfonic may be sulfated to produce thecorresponding groups to be introduced. Sulfuric acid of about sosulfuric acid esters and their salts. These sul- 100% strength can alsobeused but-in order to fates are useful as detergents, emulsifying andinsure sulfonation of the aromatic nucleus temd sp si e a e ts. t f r whh purposes they peratures above about or c. are necessary. give verysatisfactory results. It has been found, At low temperatures, about 10C. or lower, no

0 howeve t ese oduct a be improved sulfonation takes place but thealiphatic hydroxyl considerably by the additional introduction of atgroup i sulfated, After treatment with the sulleast one sulfonic acidgroup into the nucleus, fonating agent the product is neutralized withan represented y e P uc thus Obtained organic orinorganic base. The mostuseful bases are considerably more soluble in water than the a th lkalit l hydroxides r carb nates, simple sulfates,- do not precipitatecalcium or a ia, amines, hydroxy alkyl amines, and magnesium salts andmay be obtained in the form quaternary ammonium bases, Inert organic 31- of dry powders, whereas the simple sulfates when vents can b used tassist l ti during th mpl ly y are Wax-like materials which aresulfonating step. Examples of such solvents are not as readily in rp wdry Powdery ethylene dichloride, carbon tetrachloride and pepigments. Itroleum ether. 35

The sulfat s ar p pa ed y treatin th th Typical alkylated aromatic etheralcohols, alcohols of the above formula with concentrated which giveparticularly useful products accord. sulfuric acid (about 100%) at lowtemperatures. ing t th ntion ar as follows; Under these conditions nosulfonation of the p-ter-octylphenoxyethanol 4 aromatic nucleus takes.place. In order to intro- -t r-Dodecylphenoxyethanol 7 4 duce'thesulfonic acid group into the nucleus, -ter-Hexadecylphenoxyethanolhigher temperatures or sulfonating agents or p-see-Octylphenoxyethanolstronger than 100% sulfuric acid are required. rp-n-Dodecylphenoxyethanol The products obtained according to the presentr p-n-Octadecylphenoxyethanol I invention by introducing both a sulfonicacid ter-Octyl-p-naphthoxyethanol 5 group and a sulfuric acid group intothe molecule p-ter-Octylphenoxypropanol-1 of the .ether alcohol are allextremely soluble in p-ter-Octylphenoxybutanol-1 water. Most of them canbe dissolved in an equal p-ter-Octylphenoxy-propane diol-1,2 weight ofwater and the solutions thus ob- The aromatic nucleus R. can containadditional 50 tained are for the most part optically clear. In nuclearsubstituents, such as halogen, nitro, acyl, 50

the form of their water-soluble salts, such as alkyl, aralkyl,cyclo-alkyl, or aryl groups. those of the alkali metals, ammonia oramines, For example, p-ter-octyl-o-chlorphenoxythey are extremely usefulas textile assistants ethanol, p-ter-octyl-o-cresyloxyethanol,p-nitroparticularly as wetting agents and penetrants.o-sec-octylphenoxypropanol-1, p-ter-octyl-o- They are also useful asdeflocculating or dispersacetyl-phenoxyethanol,p-ter-octyl-o-benzylphenoxyethanol, pter dodecyl o cyclohexylphenoxyethanol, p-ter-octyl-o-phenylphenoxyetha- 1101, etc.- can beused. 7

The following examples are given to illustrate the invention. It is not,however, limited to the exact reagents, time, temperature and conditionsof operation shown as it may otherwise be practiced within the scope ofthe appended claims.

S OzNB 250 g. of p-u ,v-tetramethylbutylphenoxyethanol (1 mol.) iscooled to C. and stirred, while 235 g. of chlorosulfonic acid (2'mols)is gradually added, so that the temperature does not rise above 20 C.The mixture is stirred at to C. for about four hours after all the acidhas been added, and is then allowed to come to room temperature. Thethick, red sirup obtained is run onto ice and neutralized with 10%caustic soda. solution to pH 8. The clear, pale yellow, foamy, soapysolution obtained is a very powerful penetrating agent. In its acidicform it has the probable formula BOaH Instead of caustic soda, one mayuse caustic potash, ammonium hydroxide, a methylamine, mono-, diortriethanolamine or other watersoluble base to neutralize the product.The solutions obtained are useful as deflocculating agents for colloidalsulfur, zinc oxide, and other pig'- ments. The water can be evaporatedto leave the Example 2 o-cn,-c11--cH=o s 031%. 0 HE- S OaNa S 0 :NB 168g. of p-terdodecylphenoxypropane-diol- 1,2 (0.5 mol.) was dissolved in300 cc. of ethylene dichloride, and a stream of sulfur trioxide passedin at 0 to 5 C. until the gain in weight amounted to 120 g. (1.5 mols)The mixture was poured on ice'and neutralized with 10% caustic sodasolution. The clear solution obtained is useful as a penetrant orwetting agent.

In place of the ter-dodecylphenoxypropanediol-1,2, the corresponding 0-or p-sec-dodecylphenoxypropane-diol, or n-dodecylphenoxypropane-diol-1,2may be used.

These ether alcohols are obtained by condensing glycerolmonoohlorohydrin with the dodecylphenol in the presence of excesscaustic soda. The ter-dodecylphenol is obtained by condensing phenolwith tri-isobutylene in the presence of concentrated sulfuric acid as acondensing agent. The 0- and p-dodecylphenols are obtained by heatinglauryl alcohol with excess phenol at 180 to 190 C. for several hourswith anhydrous zinc chloride.

Example 3 181 g. of hexadecylphenoxyethanol (0.5 mol.) was treated with118 g. of chlorosulfonic acid (1 mol.) at 0 to 5 C., as described inExample 1. The product was neutralized with dilute potassium hydroxidesolution. The product was a very foamy, soapy solution, useful as adetergent. The sodium and ammonium salts are similar in character.

The hexadecylphenoxyethanol was derived by condensing cetyl alcohol withphenol and zinc chloride at 190 to 200 C. and reacting upon thedistilled product with excess caustic soda and ethylene chlorohydrin inalcoholic solution.

Example 4 -o-c,mo s 0.1%

Cls ar- S OaNa S OaNB 195 g. of octadecylphenoxyethanol (0.5 mol.) wastreated at 0 to 5 C. with 180 g. of chlorosulfonic acid, as described inExample 1. The red' mass obtained was allowed to stand 24 hours at 10 toC. It was then neutralized with dilute sodium hydroxide solution at 10to 15 C. The pale reddish solution obtained is useful as a detergent oremulsifying agent.

Eicample 5 51111 T sNm A mixture of 1 mol. of phenol and 2 molsofdiisobutylene was treated with 0.2 mol. of concentre-ted sulfuric acidat 25 to 30 C. for 24 hours. The oil obtained was boiled with watercontaining suflicient caustic soda to just neutralize the free acid, andthe oil layer distilled in vacuo over a small amount of soda. Thediter-octylphenol distilled over at 170 to 200 C./3 mm. as a heavy oil.This was converted to diter-octylphenoxyethanol (b. p. 160 to215 C./1mm.) by heating in alcohol with excess caustic soda and ethylenechlorohydrin.

181g. of di-ter-octylphenoxyethanol (0.5 mol.) was mixed with 150 g. offuming sulfuric acid (10% S03) at 15 to C., and stirred for eight hours.The mixture was poured on ice and neutralized with ammonium hydroxide.The solution obtained is useful as a wetting agent.

Example 6 a iv 56mm 150 g. of ter-octyl-s-naphthoxyethanol (0.5 mol.)were treated with 120 g. of chlorosulfonic acid at 5 to 10 C. for fourhours, then poured on ice and neutralized with caustic soda solution.

scream-colored powder whose aqueous solutions have a powerfulpenetrative action on cotton.

Example 7 S OaNB To 153 g. of dodecylphenoxyethanol (0.5 mol.) .therewere added, while stirring, 118 g. of chlorosulfonic acid, at atemperature between 0 and 10 C. The mixture was stirred eight hours atthis temperature and then allowed to come toroom temperature. It waspoured on ice after three hours standing at room temperature, and themixture neutralized to pH 8 with 10% caustic soda solution.' Thesolution obtained is useful as a detergent.

In a similar manner, tetradecylphenoxyethanol canbe employed.

The sulfonation products described in the foregoing examples can beemployed in acid or alkaline solution.

The specific ether alcohols employed in the foregoing examples can bereplaced mol. for mol. by any of the analogous ether alcohols heretoforementioned, or by mixtures thereof, or similar alcohol ethers in which Rof the genericformula above-shown may consist of a polyalkylene ethergroup such as the fi-mono(a,,v,' -tetramethylbutylphenyl) ether of diortriethylene glycol, etc. Ethers of this type can beprepared by heatingthe corresponding alkylated phenols having at least eight carbon atomsin the alkyl substituent, with p-chloro-p' hydroxydiethyl ether orp-chloro-ethoxy-p-hydroxydiethyl ether respectively and caustic soda; orthey may be prepared by the hydrolysis of the correspondingfl(alkylphenoxyalkoxy) -p'-chloropolyalkyl ethers.

Example 8 29.4 g. of ,8(p-a,a,-y, -tetramethylbutylphe noxy)-fi'-hydr.oxydiethyl ether were dissolved in 30 cc. of carbontetrachloride and to the solution there were added at 10 to 20 C. 24 g.of chlorosulfonic acid. After stirring for five hours at 20 to 25 C.,the solution was neutralized at 10 C. with ice-cold 10% caustic sodasolution and the solvent and water removed by evaporation. The productwas a water-soluble powder corresponding to the formula OKs-C(CHah-CHr-C(CH3):-

Its sodium, potassium or ammonium salts are extremely water-solublewhite powders.

The tertiary octylphenoxy groups of the polyalkylene ether alcohols usedin the foregoing exaliphatic carbon atoms in the chain.

ample can be replaced by any of the alkyi. substituted aryioxy groupsherein mentioned.

The products containing both sulfonic and sulfuric groups describedherein possess much greater solubility in water than the correspondingsimple sulfates having the same number of Because of their high degreeof water-solubility, these new compounds are eflective in many cases atlower concentrations than the present commercial alkyl sulfates'orsulfonates having from eight to eighteen carbon atoms in the chain.

I claim:

1. A compound having the formula SOzNa 2. A compound having the generalformula $01M in which A is an alwl group containing from eight toeighteen carbon atoms inclusive and M is a member of the groupconsisting of hydrogen, alkali metals, ammonium and substituted ammoniumradicals.

3. A compound having the general formula A-B- -OC2H40SO;M

in which A is an alkyl group containing from eight to eighteen carbonatoms inclusive, R. is one of the group consisting of benzene andnaphthalene nuclei and M is a member of the group consisting ofhydrogen, alkali metals, ammonium and substituted ammonium radicals.

4. A compound having the general formula A-R-OC:H4OB0:M

souu 1 in which A is an alkyl group containing at least eight carbonatoms, R is one of the-group consisting of benzene and naphthalenenuclei and M is a member of the group consisting of hydrogen,

alkali metals, ammonium and substituted amcarbon atoms, M is a member ofthe group consisting of hydrogen, alkali metals, ammonium andsubstituted ammonium radicals, and a: and 1! each have the value of oneor two.

6. A compound of the general formula A-l|l-O-R'(OSO|M).

gen, alkali metals, ammonium and substituted ammonium radicals, and xand 1! each have the value of one or two.

7. The process of preparing a compound of the formula SOsNa whichcomprises treating one mol. of an octylphenom ethanol with two mols of asulfonating agent and neutralizing the reaction product with sodiumhydroxide.

8. The process of producing a compound which in the acidic form has thegeneral formula.

in which A is an alkyl group containing from eight to eighteen carbonatoms inclusive, which comprises treating one mol. of an alkylatedphenoxyethanol A-CaH4OCzH4'OI-I with two mols of a sulfonating agent andneutralizing the product with a water-soluble base.

9. The process of preparing compounds which in the acidic form have thegeneral formula in which A is an alkyl radical containing from eight toeighteen carbon atoms inclusive, and R is a member of the groupconsisting of benzene and naphthalene nuclei, which comprises treatingone mol. of the alkylaryloxy ethanol .A-M-CS'HdOH with two' mols of asulfonating agent.

10. The process of preparing compounds which in the acidic form have thegeneral formula ARO -C 2114-08 02E in which A is an alkyl radicalcontaining at least eight carbon atoms, and R is a member of the [groupconsisting of benzene and naphthalene in which A is an alkyl radicalcontaining fromeight to eighteen carbon atoms inclusive, R is a memberof the group consisting of benzene and naphthalene nuclei, R is a memberof the group consisting of alkylene radicals containing at leasttwocarbcn atoms and polyalk-ylene ether radicals in which the alkylenegroups contain at least two carbon atoms, and a: and 1! each have thevalue one or two, which comprises treating one moi. of an alkylatedphenoxy alkylol A-R-Q-R/(OH): with (x+y) mols of a sulfonating agent,and neutralizing the product with a water-soluble base.

12. The process of preparing compounds which in the acidic form have thegeneral formula in which A is an alkyl radical containing at least eightcarbon atoms, R is a member of the group consisting of benzene andnaphthalene nuclei, R is a member of the group consisting of alkyleneradicals containing at least two carbon atoms and polyalkylene etherradicals in which the alkylene groupscontainat least two carbon atoms,and :c and g each have the value one or two, which comprises treatingone mol. of an alkylated phenoxy alkylol A--R-O-R'(OH) with (2+ mols ofa sulfonating agent, and neutralizing the product with a water-solublebase.

13. A, compound having the formula soma 14. A compound having theformula HERMAN A. BRUSON.

